Trisubstituted hydrazines

ABSTRACT

Trisubstituted hydrazines having the general formula (I): in which R and R1 each denotes an alkyl, cycloalkyl, aralkyl or aryl radical or together with the nitrogen atom may denote a heterocyclic ring and R2 denotes an Alpha , Beta - or Beta , gamma -unsaturated aliphatic hydrocarbon radical or an arylmethyl radical (with the exception of compounds in which R, R1 and R2 are identical). They are valuable growth regulators in their quaternized form.

United States Patent Koenig 154] TRISUBSTITUTED HYDRAZINES [72]Inventor: Karl-Heinz Koenig, Frankenthal,

Germany [73] Assignee: Badische Anilin- &Soda-Fabrik Aktiengesellschaft,Ludwigshafen/ Rhine, Germany 221 Filed: Feb. 18, 1969 [21] Appl.No.:800,244

[30] Foreign Application Priority Data Feb. 28, 1968 Germany ..P 16 68872.5

[52] US. Cl. ..260/583 B, 7l/88, 71/92, 71/94, 71/106, 71/121, 260/247,260/247.7

A, 260/293 R, 260/294.7 H, 260/326.86,

[51] Int. Cl C07c 109/00, C07c 109/02,

C07c 109/04 [58] Field of Search ..260/583 B, 584 C [56] ReferencesCited UNITED STATES PATENTS 9/1969 Jung et a1. ..260/583 B [1513,683,026 1 Aug. 8, 1972 Primary Examiner-Joseph Rebold AssistantExaminer-Richard L. Raymond Attorney-Johnston, Root, OKeeffe, Keil,Thompson & Shurtleff ABSTRACT in which R and R each denotes an alkyl,cycloalkyl, aralkyl or aryl radical or together with the nitrogen atommay denote a heterocyclic ring and R denotes an a,B- or [fly-unsaturatedaliphatic hydrocarbon radical or an arylmethyl radical (with theexception of 1 compounds in which R, R and R are identical). They arevaluable growth regulators in their quatemized form.

9 Claims, No Drawings TRISUBSTITUTED HYDRAZINES The present inventionrelates to trisubstituted hydrazines having the general formula (I):

in which R and R each denotes an alkyl, cycloalkyl, aralkyl or arylradical or together with the nitrogen atom may denote a heterocyclicring and R denotes an a,B- or B;y-unsaturated aliphatic hydrocarbonradical or an arylmethyl radical (with the exception of compounds inwhich R, R and R are identical), and to a process for the production oftrisubstituted hydrazines. The compounds are valuable growth regulatorsin the form of the quaternized hydrazines.

I have found that hydrazines having the general formula (I):

in which R and R each denotes an unsubstituted or substituted alkyl,cycloalkyl, aralkyl or aryl radical or together with the nitrogen atomdenote a heterocyclic ring and R denotes an unsubstituted or substituteda,B- or B,'y-unsaturated aliphatic hydrocarbon radical or an arylmethylradical can be prepared in a simple manner by treating with a basicreagent a hydrazinium salt having the general formula (II):

in which R and R have the above meaningsand R has the meaning givenabove for R (with the exception of the unsubstituted or substituteda,,B-unsaturated aliphatic hydrocarbon radical) or may also denote analkyl radical bearing as substituent in B-position a halogen atom,preferably a chlorine atom or a bromine atom, or an alkyl or arylsulfonyloxy group and X" denotes an inorganic or organic anion.

The alkyl radical R or R may advantageously be one having one to 18,preferably one to 10, and particularly one to six carbon atoms. They maycontain inert substituents such as aryl or methoxy groups,but alkylradicals are preferred. R and R may also form together with the nitrogenatom a ring which preferably contains five to seven members and which inaddition to the nitrogen atom may also contain another hetero atom, forinstance an oxygen atom, for example the radical of piperidine,morpholine or pyrrolidine.

Aromatic hydrocarbon radicals R and R preferably contain up to 10,particularly up to six, carbon atoms in the ring system and may alsobear inert substituents, for example halogen atoms, alkyl, aryl, alkoxyor aroxy groups.

a ,B-unsaturated aliphatic hydrocarbon radicals R advantageously containfrom two to eight, particularly from two to six, carbon atoms and maybear inert substituents such as alkoxy, aroxy or carbalkoxy groups.Examples of such radicals R are l-phenylvinyl, 2-carbomethoxyvinyl,2-phenoxyvinyl and particularly the vinyl radical.

,B,y-unsaturated aliphatic hydrocarbon radicals R and R generallycontain three to 12, preferably three to six, carbon atoms and may bearinert substituents such as alkoxy, carbalkoxy, aryloxy groups andparticularly halogen atoms. Examples of such radicals are the allyl,methallyl, 2-chloroallyl, 2,3,3-trichlo'roallyl, 2- carbomethoxyallyland 2-methoxyallyl radicals.

Suitable arylmethyl radicals R are especially those containing up to 15carbon atoms and they may contain in the aromatic ring inertsubstituents such as halogen atoms, alkyl, aryl, alkoxy or aroxy groups.The use of phenylmethyl radicals is preferred. Examples are: the benzyl,p-methoxybenzyl and a-naphthylmethyl radicals.

Suitable alkyl radicals R which bear a halogen atom or an alkyl or arylsulfonyloxy group as substituent in [3- position and which containgenerally from two to eight, preferably from two to six, carbon atoms inthe alkyl radical are, for example, the 2-chloroethyl, 2- bromoethyl,2-(phenylsulfonyloxy)-ethyl, 2-(methylsulfonyl-oxy)-ethyl and2-(p-toluenesulfonyloxy)-ethyl radicals.

The hydrazinium salts (II) to be used as starting materials canadvantageously be prepared in known manner by reaction ofN,N-disubstituted hydrazines with suitable alkylating agents. Thestarting materials (II) therefore contain in general an anion X" whichoriginates from the alkylating agent.

Starting materials (II) may of course .be used in which the anionoriginating from an alkylating agent has been replaced by any otherinorganic or organic anion.

Examples of suitable anions X are the halide, sulfate, phosphate,perchlorate, tetrafluoroborate, acetate, benzoate andnitrate anions andalso anions of methylsulfuric acid, arylsulfonic acids or alkylsulfonicacids.

It is preferred to use starting materials in which R denotes anunsubstituted or substituted allyl radical. Examples of startingmaterials II) are:

N,N-diisobutyl-N-(p-methoxybenzyl)-hydrazinium chloride,

N,N-diethyl-N-allylhydrazinium chloride,

N-phenyl-N-n-hexyl-N-methallylhydrazinium bromide,

N-phenyl-N-n-octadecyl-N-(2-chloroallyl)- hydrazinium bromidemorpholyl-N-(2-bromoethyl)-hydrazinium bromide,

N-cyclohexyl-N-ethyl-(2-methylsulfonyloxyethyl)- hydraziniummethane-sulfonate andN-(p-methoxyphenyl)-N-isopropyl-N-allylhydraziniumchlon'de.

Both inorganic bases such as alkali metal oxides or hydroxides, alkalineearth oxides or hydroxides, alkali metal carbonates or bicarbonates andorganic bases, preferably tertiary amines and particularly those havingat least two lower alkyl groups on the nitrogen atom orheterocyclic-aromatic amines, are suitable for the treatment of thestarting materials (II) with basic reagents. Examples are sodiumhydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate,potassium, carbonate, triethylarnine, triethanolamine,dimethylcyclohexylarnine, dimethylaniline and pyridine; for the reactionof starting materials in which R denotes a [Ry-unsaturated alkylradical, primary or secondary amines such as monomethylamines,

cyclohexylamines, aniline, dimethylamine or methylaniline are alsosuitable. The hydrazinium salt and the basic reagent are generallyreacted in a ratio of from 1:1 to 1:3.

When hydrazinium salts (II) in which R is an alkyl radical bearing ahalogen atom or an alkyl or aryl sulfonyloxy group in B-position as asubstituent are used in the process according to this invention, thecorresponding hydrazines generally cannot be formed but end products inwhich R is an a,,B unsaturated hydrocarbon radical are immediatelyobtained, hydrogen halide or an alkyl or arylsulfonic acid beingeliminated. Since these end products are as a rule thermally unstable,they are advantageously isolated in the form of the correspondinghydrazinium salts. These may be obtained for example by using about 1 to2 moles of base for each mole of starting material for the rearrangementof the starting material in question.

The reaction is advantageously carried out in a solvent. Polar solvents,particularly those which are miscible with water, are generally used;examples are alcohols, ethers, nitriles, amides, sulfoxides and water.Specific examples are: methanol, ethanol, dioxane, acetonitrile,dimethyl formamide, N-methylpyrrolidone and dimethyl sulfoxide. It ispreferred to use water alone as the solvent.

The process according to this invention is advantageously carried out ata temperature of from 20 to +1 50 C, preferably from to +90 C. Thereaction is generally carried out at atmospheric pressure.

The reaction is carried out for example by adding an aqueous solution ofthe basic reagent to an aqueous solution of the hydrazinium salt at thereaction temperature. The isolation of the end product may be carriedout for example by distilling the reaction mixture or by extracting thereaction mixture with an inert solvent followed by fractionaldistillation of the extract. Examples of extracting agents are aromaticand aliphatic hydrocarbons (which may be nitrated or halogenated) suchas methylene chloride, trichloroethylene, chloroform, chlorobenzene,nitrobenzene, petroleum ether, ligroin, cyclohexane, benzene, toluene,xylene or tertiary amines such as N,N-dimethylcyclohexylamine,dimethylaniline, quinoline and triisopropylamine. The substitutedhydrazines which are richer in carbon and more sparingly soluble inwater often separate as a second layer after alkali has been addedrendering the use of an extraction agent unnecessary.

Since the hydrazinium salts to be used in the process according to thisinvention are generally obtained by alkylation of N,N-di-substitutedhydrazines or by reaction of tertiary amines with chloroamine orhydroxylamine-O-sulfonic acid, a preferred embodiment of the process isto carry out the alkylation of the N,N-disubstituted hydrazine or thequatemization of the tertiary amine and subsequent treatment of thehydrazinium salt formed with a basic reagent in the same reactor. Thealkylation or quatemization is preferably carried out in the samesolvent in which the further reaction of the hydrazinium salt formed iseffected. Alkylating agent and N-N-di-substituted hydrazine arepreferably reacted in a molar ratio of 1:1 and reaction temperatures offrom 10 to 120 C are generally used. The end products are valuablepharmaceuticals and plant protection agents. In the form of quatemizedhydrazines they are valuable growth regulators for cereal crops.

The invention is illustrated by the following examples, in which theparts are parts by weight.

EXAMPLE 1 A solution of 40 parts of sodium hydroxide in 200 parts ofwater is dripped at room temperature into a mixture of 159 parts of a 50percent by weight aqueous solution ofN,N-dimethyl-N-(,B-chloroethyl)-hydrazinium chloride and the reactionmixture is stirred for 12 hours at room temperature and for another 3hours at 60 C. The water is then distilled off at subatmosphericpressure. The crystalline residue is freed from the sodium chlorideformed by boiling with alcohol. The alcoholic solution is evaporated ona water bath and the crude product obtained is recrystallized from amixture of alcohol and acetone. Eighty-seven gram (70.5 percent of thetheory) of N,N-dimethyl-Nvinylhydrazine hydrochloride is obtained havinga melting point of 165 C.

EXAMPLE 2 A solution of 58 parts of sodium hydroxide in 150 parts ofwater is allowed to drip at.20 to 25 C into a solution of 170 parts ofN,N-dimethyl-N-allylhydrazinium chloride in 100 parts of water. Thereaction mixture is stirred for 3 hours at room temperature and foranother hour at 50 to 60 C using an efficient reflux condenser. Onehundred parts of concentrated hydrochloric acid is then added and thesolution obtained is evaporated to dryness. Fifty percent by weightcaustic soda solution is added to the residue while cooling until analkaline reaction is obtained. A very concentrated solution is obtainedwhich is extracted several times with methylene chloride in the cold.The methylene chloride is then distilled off. A fraction of parts (80percent of the theory) of N,N-dimethyl-N'-allylhydrazine is obtainedhaving a boiling point of from 100to 102C at2l mm.

EXAMPLE 3 121 parts of allyl bromide is dripped at from 30 to 35 C intoa solution of 60 parts of N,N-dimethylhydrazine in 70 parts of water. Asolution of 58 parts of potassium hydroxide in 100 parts of water isthen dripped in at 25 C. After 2 to 3 hours the aqueous solution isroughly distilled in vacuo and the fraction containing the end productis dried over caustic soda. After another distillation, parts (85percent of the theory) of N,N-dimethyl-N-allylhydrazine is obtainedhaving a boiling point of from 96 to 97 C at 19 mm.

EXAMPLE 4 Ninety parts of methallyl chloride is dripped at from 35 to 40C into a mixture of 60 parts of N,N-dimethylhydrazine and 60 parts ofacetonitrile. The resultant semicrystalline product is stirred foranother 2 hours, the acetonitrile is removed in a weak vacuum and 60parts of concentrated sodium carbonate solution is dripped in. The wholeis heated for 3 hours at from 50 to 60 C, the aqueous solution formed isdistilled in a water jet vacuum and the fraction containing the endproduct is dried over caustic potash. After another EXAMPLE 5 A solutionof 22 parts of sodium hydroxide in 88 parts of water is dripped at 20 to25 C into a solution of 95 parts of N,N-dimethyl-N-(2-chloroallyl)-hydrazinium chloride in 80 parts of water. The reaction mixture isheated for 2 hours at from 50 to 60 C; an acid reaction is set up byadding concentrated hydrochloric acid and the whole is evaporated todryness in vacuo. Sixty three parts of 50 percent by weight caustic sodasolution is added to the residue. Then extraction is carried out andrepeated several times with chloroform in the cold. Sixty two parts ofN-(2- chloroallyl)-N,N-dimethylhydrazine having a boiling point of from48 to 50 C at 20 mm is obtained by fractional distillation.

EXAMPLES 6 TO 9 These are carried out analogously to Example 5. ExExample No; SHC starting hydrazinium chloride; Y yield in percent; BPboiling point in C at the pressure in mm given in parenthesis.

Ex SHC End product Y BP 6 N,N-diisopr0pyl- N,N-diisopropyl- 83 155-157N-allyl N"allylhydrazme 19) 7 N,N-dicyclohexyl- N,N-dicyclohexyl- 9498-99 N-methallyl N"-methallyl hy- (2) drazine 8 N,N-dimethyl-N-N,Ndimethyl-N"- 42 1 12-1 13 benzyl benzylhydrazine (l8) 9 N-phenyl-N-methyl- N-phenyl-N-methyl- 79 121-l24 N-allyl N"-allylhydrazine (23)Examples 10 to 13 are carried out according to the method given inExample 4.

EXAMPLEIO Starting materials: N-aminohexamethylenimine and allylchloride;

End product: N-allyl-N--hexamethylenehydrazine;

Boiling point: 45 to 46 C at 0.1 mm;

EXAMPLE 1 1 Starting materials: N-aminohexamethylenimine and2-ch1oroal1yl chloride; End product:

amethylenehydrazine; Boiling point: 80 to 82 C at 0.5 mm; n 1.4978.

EXAMPLE 12 Starting materials: N-aminohexamethylenimine and methallylchloride; End product:

amethylenehydrazine; Boiling point: 42 to 44 C at 0. 1 mm; n 1.4893.

EXAMPLE 13 Starting materials: N,N-dimethylhydrazine and 1,2-

dibromoethane;

6 End product: N,N-dimethyl-N-vinylhydrazinium bromide; "Melting point:1 15 C.

I claim: 1. A trisubstituted hydrazine having the formula:

in which R and R each denotes an alkyl group having one to 18 carbonatoms, and R denotes an a, B- or B, y-unsaturated aliphatic hydrocarbongroup, or said un saturated hydrocarbon groups substituted with alkoxy,or said ,8, 'y-unsaturated hydrocarbon group substituted by halogen.

2. A trisubstituted hydrazine as claimed in claim 1 wherein R denotes ana, ,B-unsaturated aliphatic hydrocarbon group with two to eight carbonatoms or a B, y-unsaturated aliphatic hydrocarbon group with three to 12carbon atoms.

3. A trisubstituted hydrazine as claimed in claim 1 wherein R denotesallyl, methallyl, chloro-substituted allyl, or methoxyallyl.

4. A trisubstituted hydrazine as claimed in claim 1 wherein R denotesvinyl.

5. A process for the production of a hydrazine having the generalformula:

in which R and R each denotes an alkyl group having one to 18 carbonatoms and R denotes an a, B- or B, 'yunsaturated aliphatic hydrocarbongroup, or said unsaturated hydrocarbon groups substituted with alkoxy,or said ,B,'y-unsaturated hydrocarbon group substituted by halogen;which comprises treating with a basic reagent a hydrazinium salt havingthe general formula in which R and R have the above meanings and R hasthe meanings specified for R with the exception of said a,BB-unsaturatedaliphatic hydrocarbon radical or denotes an alkyl group bearing assubstituent in B-position a halogen atom, or an alkyl or arylsulfonyloxy group and X" denotes an inorganic or organic anion.

6. A process as claimed in claim 5 wherein R denotes an a, B-unsaturatedaliphatic group hydrocarbon with two to eight carbon atoms or aLivy-unsaturated aliphatic group hydrocarbon with three to 12 carbonatoms.

7. A process as claimed in claim 5 wherein R denotes allyl, methallyl,chloro-substituted allyl, methoxyallyl, or vinyl.

8. A process as claimed in claim 5 wherein R denotes an alkyl grouphaving two to eight carbon atoms and substituted in B-position bychloro, bromo, phenylsulfonyloxy or methyl-sulfonyloxy.

9. A process as claimed in claim 5 wherein R denotes allyl, methallyl,chloroallyl or methoxyallyl.

2. A trisubstituted hydrazine as claimed in claim 1 wherein R2 denotesan Alpha , Beta -unsaturated aliphatic hydrocarbon group with two toeight carbon atoms or a Beta , gamma -unsaturated aliphatic hydrocarbongroup with three to 12 carbon atoms.
 3. A trisubstituted hydrazine asclaimed in claim 1 wherein R2 denotes allyl, methallyl,chloro-substituted allyl, or methoxyallyl.
 4. A trisubstituted hydrazineas claimed in claim 1 wherein R2 denotes vinyl.
 5. A process for theproduction of a hydrazine having the general formula: in which R and R1each denotes an alkyl group having one to 18 carbon atoms and R2 denotesan Alpha , Beta - or Beta , gamma -unsaturated aliphatic hydrocarbongroup, or said unsaturated hydrocarbon groups substituted with alkoxy,or said Beta , gamma -unsaturated hydrocarbon group substituted byhalogen; which comprises treating with a basic reagent a hydraziniumsalt having the general formula in which R and R1 have the abovemeanings and R3 has the meanings specified for R2 with the exception ofsaid Alpha , Beta Beta -unsaturated aliphatic hydrocarbon radical ordenotes an alkyl group bearing as substituent in Beta -position ahalogen atom, or an alkyl or aryl sulfonyloxy group and X( ) denotes aninorganic or organic anion.
 6. A process as claimed in claim 5 whereinR2 denotes an Alpha , Beta -unsaturated aliphatic group hydrocarbon withtwo to eight carbon atoms or a Beta , gamma gamma -unsaturated aliphaticgroup hydrocarbon with three to 12 carbon atoms.
 7. A process as claimedin claim 5 wherein R2 denotes allyl, methallyl, chloro-substitutedallyl, methoxyallyl, or vinyl.
 8. A process as claimed in claim 5wherein R3 denotes an alkyl group having two to eight carbon atoms andsubstituted in Beta -position by chloro, bromo, Phenylsulfonyloxy ormethyl-sulfonyloxy.
 9. A process as claimed in claim 5 wherein R3denotes allyl, methallyl, chloroallyl or methoxyallyl.